Green Chemistry and Commercial Applications

John C. Warner

President and Chief Technology Officer Warner Babcock Institute for Green Chemistry, LLC

President Beyond Benign

[email protected]

JohnWarnerOrg The Poisoning of America

Chicago’s Toxic Air

BISPHENOL A

BROMINATED FLAME RETARDANTS

PHTHALATES Asking the Right Questions

Why would a chemist make a hazardous material?

How do we train chemists? UMASS Boston – 1980-1984

Professor J.-P. Anselme . "N-Nitrosamines from the Reaction of N-Chlorodialkylamines with Sodium Nitrite." Nakajima, M.; Warner, J. C.; Anselme, J.-P. J. Chem. Soc., Chem. Commun., 1984, 451. . "N-Nitrosamines via the Phase-Transfer mediated Nitrosation of Secondary Amines with Sodium Nitrite and N-Haloamides." Nakajima, M.; Warner, J. C.; Anselme, J.-P. Tetrahedron Lett., 1984, 25, 2619. . "N-Nitrosamines from the Reaction of Sulfamoyl Chlorides with Sodium Nitrite." Warner, J. C.; Nakajima, M.; Anselme, J.-P. Bull. Soc. Chim. Belges, 1984, 93, 919. . "The Wittig Reaction in the Undergraduate Organic Laboratory." Warner, J. C.; Anastas, P. T.; Anselme, J.-P. J. Chem. Ed., 1985, 62, 346. . "Benzoyl Phenyl 1-Methylpyrazoles. Synthesis, Characterization, and Spectra." Kano, K.; Scarpetti, D.; Warner, J. C.; Anselme, J.-P.; Springer, J. P.; Arison, B. H. Can. J. Chem., 1986, 64, 2211. Princeton University – 1984-1988

Professor E. C. Taylor . "Diels-Alder Reactions of Bicyclic 1,2,4-Triazines: The Conversion of Pyrimido[4,5-e]-1,2,4-triazines to Pyrido[2,3-d]pyrimidines." Taylor, E. C.; McDaniel, K. F.; Warner, J. C. Tetrahedron Lett., 1987, 28, 1977. . "Synthesis and Structural Confirmation of 5,6-Cyclopenteno-5-deazapterin." Taylor, E. C.;Warner, J. C., Heterocycles, 1987, 26, 2673. . "Heterodienophilic Intramolecular Diels-Alder Reactions of 1,2,4-Triazines. Synthesis of Novel Polycyclic Condensed Pyrazines and Lumazines." Taylor, E. C.; Pont, J. L.; Warner, J. C., Tetrahedron.; 1987, 43, 5159, 1988, 44, 1825. . "Intramolecular Diels-Alder Reactions of 6-Azalumazines and 6-Azapterins. A Facile Route to 6,7-Annulated-5-deazapteridines." Taylor, E. C.; Warner, J. C.; Pont, J. L., J. Org. Chem., 1988, 53, 800. . "Diels-Alder Reactions of 7-Azalumazines. Synthesis of Condensed Lumazines and 8-Deazalumazines" Taylor, E. C.; Warner, J. C.; Pont, J. L., J. Org. Chem., 1988, 53, 3568. . "Diels-Alder Reactions of 6-Azapterins. An Alternate Strategy for the Synthesis of 5,10 Dideaza-5,6,7,8-tetrahydrofolic Acid (DDATHF)." Taylor, E. C.; Harrington, P. M.; Warner, J. C., Heterocycles, 1988, 27, 1925. . "Aromatic-Aromatic Interactions in Molecular Recognition: A Family of Artificial Receptors for Thymine that Shows Both Face-To-Face and Edge-To-Face Orientations." Muehldorf, A. V.; Van Engen, D.; Warner, J. C.; Hamilton, A. D., J. Am. Chem. Soc., 1988, 110, 6561. . "Synthesis of 6,7-Dihydrothieno[3,2-g]-5-deazapterin." Taylor, E. C.; Pont, J. L.; Warner, J. C., J. Het. Chem., 1988, 25, 1733. . "Competitive Intramolecular Diels-Alder Reaction and Intramolecular Coplanar Cycloamination of 3-(3-Butynylthio)-1,2,4-triazin-5-ones." Taylor, E. C.; Pont, J. L.; Van Engen, D.; Warner, J. C., J. Org. Chem., 1988, 53, 5093. . "Synthesis and Competitive Thermal Reactions of 3-[2'-(2-Propynylthio)- phenylamino]-1,2,4-triazines." Taylor, E. C.; Pont, J. L.; Warner, J. C., J. Org. Chem., 1989, 54, 1456. . "New Synthetic Studies on Deazafolates." Taylor, E. C.; Chang, Z. Y.; Harrington, P. M.; Hamby, J. M.; Papadopoulou, M.; Warner, J. C.; Wong, G. S. K.; Yoon, C. M.; Shih, C., Chem. Biol. Pteridines, 1989 Proc. Int. Symp. Pteridines Folic Acid Deriv., 9th, Meeting Date 1989, 987. Ed. by: Curtius, H.-C.; Ghisla, S.; Blau, N. de Gruyter: Berlin, Fed. Rep. Ger. 1990. . "Pyridopyrimidines." Warner, John C. in "Miscellaneous Fused Pyrimidines" T. Delia, Ed. Part IV, vol. 24, pp 1-460 John Wiley, New York 1992. Polaroid Corporation – 1988-1997

Edwin Land Lloyd D. Taylor

. "Thermographic Recording Films." Dombrowski, Edward J.; Jones, Robert L.; Warner, John C.; Yang, Jiyue US Patent 5,750,463. Filed April 22, 1997. Published May 12, 1998. . “Acid-Catalyzed Thermal Decomposition of Secondary Acid Generator and Formation of Second Acid; Copper Compound and Reactive Material Used to Decompose Superacid Precursor” Marshall, John L.; Baker, Rita Shon S.; Takiff, Larry C.; Telfer, Stephen J.; Warner, John C. US Patent 5,741,630. Filed April 25, 1994. Published April 21, 1998. . “Copolymers having pendant functional thymine groups” Grasshoff, J. Michael; Taylor, Lloyd D.; Warner, John C. US Patent 5,708,106. Filed May 3, 1996. Published January 13, 1998. . “Photograph Development” Guarrera, Donna J.; Mattucci, Neil C.; Mehta, Avinash C.; Taylor, Lloyd D.; Warner, John C. US Patent 5,705,312. Filed Nov. 25, 1996. Published January 6, 1998. . “Photograph System” Guarrera, Donna J.; Mattucci, Neil C.; Mehta, Avinash C.; Taylor, Lloyd D.; Warner, John C. PCT Int. Appl. WO 1997029405. Filed January 21, 1997. August 14, 1997. DE 69701493. Filed January 21, 1997. Published April 27, 2000. EP 0820607. Filed January 21, 1997. Published January 28, 1998. . “Images by Exposure to Actinic Radiation; Solvent Removal of Non-Exposed Areas” Grasshoff, J. Michael; Taylor, Lloyd D.; Warner, John C. US Patent 5,616,451. Filed May 24, 1995. Published April 1, 1997. . “Process for Fixing an Image, and Medium for Use Therein” Ehret, Anne; Marshall, John L.; Baker, Rita Shon S.; Takiff, Larry C.; Telfer, Stephen J.; Warner, John C. US Patent 5,582,956. Filed April 28, 1994. Published December 10, 1996. . “Low-Volatility, Substituted 2-Phenyl-4,6-bis[Halomethyl]-1,3,5-triazine for Lithographic Printing Plates.” Fitzgerald, Maurice J.; Kearney, Frederick R.; Liang, Rong-Chang; Schwarzel, William C.; Guarrera, Donna, J.; Hardin, John M.; Warner, John C. PCT Int. Appl. WO 1996034315. Filed April 19, 1996. Published October 31, 1996. CA 2189459. Filed April 19, 1996. Published October 31, 1996. DE 69609136. Filed April 19, 1996. Published August 10, 2000. EP 0767932. Filed April 19, 1996. Published April 16, 1997. . “Low-Volatility, Substituted 2-Phenyl-4,6-bis[Halomethyl]-1,3,5-triazine for Lithographic Printing Plate Preparation” Fitzgerald, Maurice J.; Kearney, Frederick R.; Liang, Rong-Chang; Schwarzel, William C.; Guarrera, Donna, J.; Hardin, John M.; Warner, John C. US Patent 5,561,029. Filed April 28, 1995. Published October 1, 1996. . “Vinylbenzyl Thymine Monomers and Polymers and Products Prepared from Same” Grasshoff, J. Michael; Taylor, Lloyd D.; Warner, John C. PCT Int. Appl. WO 1995031755. Filed May 10, 1995. Published November 23, 1995. CA 2185144. Filed May 10, 1995. Published November 23, 1995. EP 0759193. Filed May 10, 1995. Published February 26, 1997. DE 69504652. Filed May 10, 1995. Published October 15, 1998. . “Process for Fixing an Image” Ehret, Anne; Marshall, John L.; Baker, Rita Shon S.; Takiff, Larry C.; Telfer, Stephen J.; Warner, John C. PCT Int. Appl. WO 95029067. Filed April 25, 1995. Published November 2, 1995. CA 2186514. Filed April 25, 1995. Published November 2, 1995. DE 69506396. Filed April 25, 1995. Published January 14, 1999. EP 0757628. Filed April 25, 1995. Published February 12, 1997. . “Vinylbenzyl Thymine Monomers and their use in photoresists” Grasshoff, J. Michael; Taylor, Lloyd D.; Warner, John C. US Patent 5,455,349. Filed May 13, 1994. Published October 3, 1995. . “Imaging Medium and Process.” Fehervari, Agota F.; Gaudiana, Russell A.; Kolb, Eric S.; Mehta, Parag G.; Taylor, Lloyd D.; Warner, John C. US Patent 5,424,268. Filed May 13, 1994. Published June 13, 1995. . “Thermally-Processable Image Recording Materials Including Substituted Purine Compounds.” Ford, Maureen F.; Guarrera, Donna J.; Mischke, Mark M.; Pai, Ramdas; Warner, John C. US Patent 5,411,929. Filed June 30, 1994. Published May 2, 1995. . "Copolymeric Mordants and Photographic Products and Processes Containing Them" Grasshoff, J. Michael; Taylor, Lloyd D.; Warner, John C. US Patent 5,395,731. Filed May 13, 1994. Published March 7, 1995. . "Process and Composition for Use in Photographic Materials Containing Hydroquinones." Taylor, Lloyd D.; Warner, John C. US Patent 5,338,644. Filed December 23, 1992. Published August 16, 1994. . “Process and Composition for Use in Photographic Materials Containing Hydroquinones." Taylor, Lloyd D.; Warner, John C. US Patent 5,177,262. Filed July 19, 1991, Published January 5, 1993. EP 0523470. Filed July 3, 1992, Published February 3, 1993. CA 2070450. Filed June 4, 1992, Published January 20, 1993. DE 69218312. Filed July 3, 1992, Published April 24, 1997. JP 06230540. Filed July 16, 1992. Non Covalent Derivatization EPA Approval Low Volume Exemption PreManufacturing Notification

“Small particles”? “Molecular Complexes”? Cambridge, MA

Washington, DC Paul Anastas

Office of Pollution Prevention and Toxics OH O

OH O OH

O O OH S

Cl O OH

OH OH

Old Technology New Technology Several Solvents Aqueous Conditions High Energies Low Energies Hazardous Reagents Non-hazardous Reagents Every Year: (United States) Chemistry and Chemical Engineering Graduates

15,000 Undergraduate Degrees

3,000 Masters Degrees

3,000 Doctoral Degrees

50.9 % Women Undergraduate Degrees (2004) To get a degree in Chemistry…

No universities require any demonstration of knowledge regarding toxicity or environmental impact! Green Chemistry is the design of chemical products and processes that reduce or eliminate the use and/or generation of hazardous substances. The Twelve Principles of Green Chemistry

1. Prevention. It is better to prevent waste than to treat or clean up waste after it is formed.

2. Atom Economy. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

3. Less Hazardous Chemical Synthesis. Whenever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment.

4. Designing Safer Chemicals. Chemical products should be designed to preserve efficacy of the function while reducing toxicity.

5. Safer Solvents and Auxiliaries. The use of auxiliary substances (solvents, separation agents, etc.) should be made unnecessary whenever possible and, when used, innocuous.

6. Design for Energy Efficiency. Energy requirements should be recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure.

7. Use of Renewable Feedstocks. A raw material or feedstock should be renewable rather than depleting whenever technically and economically practical.

8. Reduce Derivatives. Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical processes) should be avoided whenever possible .

9. Catalysis. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.

10. Design for Degradation. Chemical products should be designed so that at the end of their function they do not persist in the environment and instead break down into innocuous degradation products.

11. Real-time Analysis for Pollution Prevention. Analytical methodologies need to be further developed to allow for real-time in- process monitoring and control prior to the formation of hazardous substances.

12. Inherently Safer Chemistry for Accident Prevention. Substance and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires. Green Chemistry

More environmentally benign than alternatives

Perform better More economical than alternatives than alternatives Green Chemistry

Safety

Green Chemistry

Performance Cost UMASS – 1996-2007

1997 Assistant Professor 1998 Associate Professor (Tenure) 1999 Director of Biochemistry 2000 Full Professor 2001 Chair Chemistry Department 2001 Director Green Chemistry PhD Program 2004 Professor Plastics Engineering (UML)

Of all the products and processes…

Maybe 10% are benign…

Maybe 25% have alternatives available…

65% Still have to be invented! The cost of using hazardous materials:

Storage Transportation Treatment Disposal Regulatory Costs Liability Worker Health and Safety Corporate Reputation Community Relations New Employee Recruitment Environmental Regulations

EPACT FFCA CERFA CRAA PPA AMFA PPVA ARPAA IEREA AJA AQ ANTPA 120 ASBCAA A GLCPA ESAA-AECA ABA FFRAA CZARA FEAPRA WRDA 110 IRA EDP NWPAA NAWCA OPA CODRA/NMSPAA RECA FCRPA CAAA MMPAA GCRA 100 GLFWRA APA RCRAA WQA HMTUSA SWDA WLDI NEEA CERCLA 90 CZMIA NWPA COWLDA SDWAA FWLCA SARA MPRSAA BLRA 80 CAAA ARPA ERDDAA CWA MPRSAA EAWA SMCRA NOPPA SWRCA PTSA 70 SDWAA UMTRCA ESAA BLBA QGA FWPCA HMTA NCPA MPRSA 60 CZMA ESA TSCA NCA TAPA FLPMA FEPCA RCRA PWSA NFMA 50 MMPA FRRRPA CZMAA SOWA DPA NEPA AQA EQIA 40 FOIA FCMHSA CAA Number ofLaws Number EPA WRPA EEA AFCA OSHA FAWRAA 30 FHSA NPAA NFMUA WSRA TA EA FWCA AEPA FIFRA PAA NHPA RCFHSA BPA 20 WLDA WA FWCAA NBRA NPS MBCA FAWRA IA FWA 10 RHA AA NLRA AEA YA WPA

0 1870 1880 1890 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 WBI - 2007 ->

John Warner Amy Cannon Jim Babcock Joe Pont, CEO

100 Research Drive Wilmington, MA 01887 Fabrication & Environment Organic & Polymer Biomaterials Physical Testing, & Toxicology Synthesis Lab Lab Lab

Analytical Separations Lab

WBI Scientists …

Microscopy & Office Space Chemicals & Chemicals&

Surface Analysis LabSupplies

Applications

and and Coatings Research Lab Research

Metal Oxide Research Labs Research Oxide Metal Lab

Learning Particle Size & Surface Thermal Analysis & NMR Multi-use Chemistry

Center Lab ray

- Characterization Lab Spectroscopy Lab Lab Lab X

Beyond Benign WBI Executive Office Space Cafe

Contract Self-Funded

Invention Pharmaceutical and Invention Agricultural Products

Films Materials and Coatings and Composites

Performance Cosmetics, Personal Care Materials and Home Care Invent for collaborators Sustainability Help with commercialization Sciences Alzheimer’s Disease Therapeutic

“Dihydro-6-Azaphenalene Derivatives for the Treatment of CNS, Oncological Diseases and Related Disorders” Warner, John C.; Nguyen, Dieu; Gladding, Jeffery A.; 6 BisANS (Disaggregation) Cheruku, Srinivasa R.; Loebelenz, 5 Jean R.; Norman, James J.; Thota, 4 Sambaiah; Lee, John W.; Rosenfeld, 3

2 EC50 EC50 (uM) Craig. US Pat. Appl. US 20140094487. 1 Filed September 27, 2013. Published 0 PBT2 WBI-132WBI-143WBI-144WBI-145 April 3, 2014. PCT Int. Appl. WO Cthulhunol 2014052906. Filed September 27, 2013. Published April 3, 2014. CA 2886749. Filed September 27, 2013. Published April 3, 2014. Formaldehyde Free Wood Composites

“Lignocellulosic Compositions and Methods of Making Same” Warner, John C.; Whitfield, Justin R.; Gladding, Jeffery A.; Allen, Richard M., US Patent Filed May 26, 2015 Hair Color Restoration

Tyrosinase

Manickam Sugumaran UMASS Boston Tyrosinase

“Formulation and Processes for Hair Coloring” Warner, John C.; Muollo, Laura; Stewart, Amie US Patent Appl. 20160184197. Filed September 9, 2014. Published June 30, 2016. Appl. WO 2015057254. Filed January 25, 2015. Published April 23, 2015. US Patent 8,828,100. Filed Oct. 14, 2013. Published September 9, 2014. Ocean Plastics Recycling and Reclamation

June 29, 2015 Electronics Recycling and Reclamation

“Method for the recovery of lithium cobalt oxide from lithium ion batteries” Poe, Sarah L.; Paradise, Christopher L.; Muollo, Laura R.; Pal, Reshma; Warner, John C.; Korzenski, Michael B. US Pat. Appl. US 20140306162. Filed June 19, 2012. Published October 16, 2014.

“Sustainable process for reclaiming precious metals and base metals from electronic waste” Korzenski, Michael B.; Jiang, Ping; Norman, James; Warner, John C.; Ingalls, Laura; Gnanamgari, Dinakar; Strickler, Fred; Mendum, Ted. US Pat. Appl. US 20130336857. Filed August 19, 2011. Published December 19, 2013.

“Sustainable process for reclaiming precious metals and base metals from electronic waste” Korzenski, Michael B.; Jiang, Ping; Norman, James; Warner, John C.; Ingalls, Laura; Gnanamgari, Dinakar; Strickler, Fred; Mendum, Ted. PCT Int. Appl. WO 2012024603. Filed August 19, 2011. Published February 23, 2013. CN 103249849. Filed August 19, 2011. Published August 14, 2013. EP 2606158. Filed August 19, 2011. Published June 26, 2013.

“Non-fluoride containing composition for removal of polymers and other organic material from a surface” Korzenski, Michael B.; Jiang, Ping; Warner, John C.; Mendum, Ted; Lugus, Michelle; Whitfield, Justin; Vanbenschoten, Helen; Payne, Makonnen PCT Int. Appl. WO 2010091045. Filed Feb 3, 2010. Published August 12, 2010.

LiCoO2 Water Harvesting Technologies

Hydrophobic Hydrophilic Polaroid Corporation – 1988-1997

Edwin Land

Lloyd D. Taylor This is world’s oldest known photograph made in 1825

It was made by Joseph Nicéphore Niépce

He exposed a metal sheet coated with a material to light in a camera for 8 hours. The areas irradiated by light washed off!

The material was ASPHALT! Asphaltenes Maltenes Alzheimer’s Disease Therapeutic

Sunlight and air damage asphalt.

To repair this damage, the top layer is removed and replaced. Asphalt Compatiblizer Group

Aggregate Binding Group There is only a small amount of oxidized asphalt, but because it is localized it hurts the performance.

Delta-S is a dynamic rheology modifier.

It first helps lift of the damaged asphalt from the aggregate It then distributes and repairs the oxidative damage.

If this is all that Delta-S did, the material would remain soft and never harden.

But the dynamic rheology modifier then reverses behavior and helps re-establish the bonding of the asphalt to the aggregate. The aggregate is returned to its original state, but now has Delta-S built in to add added future stability. Construction Materials: Asphalt Paving

Monday, November 25, 2013 17oF > 60% Recycled Material

“Asphalt Binder Additive Compositions and Related Materials” Warner, John C., Muollo, Laura R.; Walker, Rowan L., Bianchini, J. R. PCT Int. Appl. WO 2015070180. Filed November 10, 2014. Published May 14, 2015. Delta-S EcoSeal Innovation & Creativity

We are successful not IN SPITE of green chemistry

But BECAUSE of green chemistry [email protected]

JohnWarnerOrg